CN107001742A - Compositions of vulcanize rubbers - Google Patents
Compositions of vulcanize rubbers Download PDFInfo
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- CN107001742A CN107001742A CN201580065889.4A CN201580065889A CN107001742A CN 107001742 A CN107001742 A CN 107001742A CN 201580065889 A CN201580065889 A CN 201580065889A CN 107001742 A CN107001742 A CN 107001742A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The present invention relates to a kind of compositions of vulcanize rubbers, the rubber composition includes at least one ethylene-alpha-olefin non-conjugated diene copolymer at least 300 with the following for 100 parts of oil-filled copolymer compositions i) a) being made up of the following, what 000g/mol weight average molecular weight (Mw) was measured in dimethylbenzene at 70 DEG C is higher than 4, preferably higher than 4.2 inherent viscosity, and the polydispersity (Mw/Mn) less than 3, preferably less than 2.8, particularly less than 2.6；Ii) the extending oil of every 100 parts by weight parts by weight of ethene o olefin unconjugated diene copolymers (i) 30 to 70, and iii) every 100 parts by weight ethene o olefin unconjugated diene copolymers (i) are up to the auxiliary agents of 5 parts by weight, thus the oil-filled copolymer compositions have the phase angle 5min less than 2.5, b) unsaturated rubber for being named as R rubber according to DIN/ISO 1629 of the every parts by weight of 100 parts by weight 1 to 15 of ethene o olefin unconjugated dienes (i) based on the oil-filled copolymer compositions a), c) filler of the every parts by weight of 100 parts by weight 30 to 100 of ethene o olefin unconjugated dienes (i) based on the oil-filled copolymer compositions a), d) the operation oil of the every parts by weight of 100 parts by weight 0 to 30 of ethene o olefin unconjugated diene copolymers (i) based on said composition a), with the proviso that the total amount of extending oil and operation oil from said composition a) is no more than the every parts by weight of 100 parts by weight 80 of ethylene-alpha-olefin non-conjugated diene copolymer (i) based on said composition a), and e) vulcanizing agent.
Description
The present invention relates to containing certain oil-filled ethylene-alpha-olefin-nonconjugated diene copolymers composition and according to DIN/
ISO 1629 be named as the unsaturated rubber of R rubber vulcanize (vulcanizable) rubber composition and its vulcanization system
Product, specifically engine bracket or be intended to be used in dynamic application in other products, such as flexible coupling and torsional vibration damper are also
There are belt, muffler suspension bracket, air spring and bridge seat.
Ethene-alpha-olefin elastomer, especially Ethylene-Propylene-Diene trimer (EPDM) are considered as varied
Application in useful excellent general purpose resilient body.
EPDM is made up of ethene and propylene recurring units with smaller amount diene units, so as to introduce unsaturation and by
This promotes the crosslinking of polymer chain.Due to being substantially absent from unsaturation in the main polymer chain, EPDM rubber is shown
Outstanding oxidation, ozone and tolerance to climate, and the more preferable heat ageing compared with conjugated diene rubber.In addition, EPDM rubber
It is advantageously comparable with many other elastomers in cost, and allow the filler and oil of high concentration while keeping good thing
Manage characteristic.For those reasons, ethene-alpha-olefin elastomer, particularly EPDM individually or with other elastomers are total to
It is widely used in many applications mixedly, including such as flexible pipe, seal, pad, roof Material and sealing strip.
However, the known of EPDM materials has the disadvantage their performances poor in dynamic application.In this regard, dynamic should
With being that wherein molded component is subjected to those of alternate stress and dynamic load and applied.Unfortunately, it is known that in such application ethene-
Alpha-olefin elastomer only shows moderate dynamic fatigue resistance, wearability, tensile strength and modulus.In these characteristics
Some are even intended to be opposite, so that being difficult to improved rubber compound.For example, curing rubber is increased
Crosslink density generally contributes to reduce compressive deformation, but also results in the tearing strength of reduction.
For EPDM polymer, peroxide cure be commonly used to substitute sulfur curable so as to further improve thermal ageing properties,
Reduction compressive deformation and the adhesiveness for being improved to processing and untreated textile.Unfortunately, the rubber of peroxide cure
Dynamic characteristic generally than sulfur curable rubber even it is worse.The fact that reduce further EPDM compounds dynamically should
Usability in.The invention provides a kind of solution for the commodity for being additionally operable to peroxide cure.
As a result, in dynamic application (such as dynamic conveyor belt, Flat belt, flexible coupling, torsional vibration damper, air bullet
Spring, engine bracket and the like) in using EPDM therefore be quite limited, especially for the chemical combination of peroxide cure
For thing, such as in WO96/13544.
The part of these types is most-often used elastomer (such as natural rubber with outstanding dynamic mechanically characteristic on the contrary
Glue, SBR styrene butadiene rubberses, polychlorobutadiene and its blend) manufacture.Specifically, natural rubber is lured due to its strain
The crystallization led is performed better than in dynamic application, but it lacks heat and ozone tolerance.
Although these polymer provide acceptable performance and show good machinability, exploitation will be highly desirable to
It is a kind of to show enough dynamic mechanically durability to allow the EPDM rubber being used in above-mentioned dynamic application.
In order to meet this purpose, EPDM is blended to open with showing the other elastomers of more favourable mechanical property
Sending out a kind of has the rubber of improved dynamic characteristic.These elastomers include polychlorobutadiene, diene rubber and organic-poly-
Silicone resin.In this case, EPDM is added to improve heat, ozone or oxygen tolerance while keeping or reducing and be final
The cost of composition.
The validity of these compounds is limited by the fact that：For producing the chemical combination with acceptable mechanical property
The ratio for the EPDM that thing can be used is fairly limited.In addition, the processing of such compound is often troublesome and held high
Expensive.
In addition, the condition required for the acceptable solidification of EPDM and the other elastomers that can be used often conflicts.
The poor miscibility and solidification incompatibility of EPDM and highly undersaturated diene rubber are by resulting composition in ess-strain
Poor performance is confirmed in experiment.In fact, such composition generally shows further worsened than any straight polymer.This
The performance section for planting difference is attributed to several factors.One reason is the difference of rate of cure.It is a kind of optimal in these rubber
Vulcanization will often cause alternative poor vulcanization.Surmount the preferred of another polymer with reference to for a kind of polymer
Different accelerators, this makes it difficult to realize satisfactorily vulcanizes for both polymer.Cause second of the vulcanization of difference
Factor is to be difficult to realize uniform disperse between two kinds of rubber.Significantly, different solubility parameters produces poor between rubber
Compatibility so that cause attempt by such rubber mix be uniform dispersion when difficulty.This produces to have and not advised
Then and non-homogeneous characteristic uneven product.Traditional bulking agent such as terpene resin and surface-active low-molecular weight polymer exist
It is not effective for relaxing in this incompatibility.
In another approach, test various additives in EPDM compounds to improve its tensile strength and resistance to tired
Lao Xing.The amount of increase reinforcing filler and peroxide has shown that carrying for both the hardness and modulus of final rubber
It is high.However, the increase of filler also has shown that the corresponding reduction of the dynamic flex fatig resistance of obtained product.This
Outside, the high level of peroxide may reduce the tearing strength of final products.The zinc salt of (methyl) acrylic acid has also been added
Into EPDM to attempt to improve wearability, tensile strength, modulus and the life-span of the elastomer under dynamic loading conditions, referring to example
Such as WO96/13544 and EP964030.This method is limited to peroxide cure and may negatively affect these compressed shapes
Become.Another has the disadvantage the limited compatibility of such zinc salt and uncured EPDM, and this make it that mixing is extremely difficult.
A common problem for all these methods be they need extra costs and/or these compounds be to
Processing is relatively difficult to less.
Therefore, it is still necessary to a kind of to show outstanding stretching and tearing strength while maintaining weather, heat, oxygen and ozone tolerance
Property and the EPDM rubber easy to process and average costs for being suitable for dynamic application.
In WO03/020806, different EPDM is used for produce rubber for dynamic application, wherein it is used this
A little rubber are oil-filled intermediate molecular weight elastomers.However, the dynamic characteristic of the vulcanizate relative to them, disclosed is poly-
Compound still shows improved space.
In US6716931, being referred to the oil-filled EPDM with 3 to 5 comparatively wide polydispersity is used for dynamic application.
The vulcanizate being made up of this polymer with wide molecular weight distribution has the disadvantages that they have deterioration dynamic special
A large amount of free suspension end of the chains of property.
In EP621309, oil-filled EPDM has 2.8 to 3.7 EPDM inherent viscosity (in dimethylbenzene, 70
DEG C) and 30phr to 50phr oil content.Due to, without using reactivator, being described in this patent in the catalyst system
These rubber also have the disadvantages that, as example referred in EP994906, they are uneven and with relative
High is branched.
In EP 13173470.9 (application number), having disclosed the modified EDPM compositions of certain oil is used for dynamic answer
With.
So far, following ethene-alpha-olefin elastic composition is not yet known, the elastic composition is to be easily worked
, and there is in dynamic application enough and heat-staple mechanical property, and the elastic composition is that height has bullet
Property, with excellent isolation characteristicses, main foundation elastic composition can be used as in applying below：Such as support,
Particularly engine bracket, belt (including dynamic conveyor belt and Flat belt), air spring and analog.
Therefore, used it is an object of the present invention to provide a kind of oil-filled EPDM rubber in the product for be subjected to dynamic load
Make base elastomeric composition, the base elastomeric composition has good vibration damping, good aging, excellent dynamic special
Property, low tan δ and appropriate mechanical property.
This purpose realizes that said composition is included by vulcanizable composition
A) the oil-filled copolymer compositions being made up of the following
I) 100 parts of at least one ethylene-alpha-olefin-nonconjugated diene copolymers with the following
- at least 300,000g/mol weight average molecular weight (Mw)
- measured in dimethylbenzene at 70 DEG C higher than 4, be preferably higher than 4.2 inherent viscosity, and
- be less than 3, be preferably less than 2.8, particularly less than 2.6 polydispersity (Mw/Mn)；
Ii) the extending oil of every 100 parts by weight ethylene-alpha-olefin-nonconjugated parts by weight of diene copolymers (i) 30 to 70
(extender oil), and
Iii) every 100 parts by weight ethylene-alpha-olefin-nonconjugated diene copolymers (i) are up to the auxiliary agent of 5 parts by weight,
Thus the oil-filled copolymer compositions have the phase angle δ less than 2.5min,
B) every 100 parts by weight 1 of ethylene-alpha-olefin-nonconjugated diene (i) based on the oil-filled copolymer compositions a) to
15th, the unsaturated rubber for being named as R rubber according to DIN/ISO 1629 of preferably 2 to 10 parts by weight,
C) every 100 parts by weight 30 of ethylene-alpha-olefin-nonconjugated diene (i) based on the oil-filled copolymer compositions a)
To the filler of 100 parts by weight,
D) it is based on said composition a) the every weight of 100 parts by weight 0 to 30 of ethylene-alpha-olefin-nonconjugated diene copolymers (i)
The operation oil of part, with the proviso that the extending oil from said composition a) and the oily total amount of operation are no more than based on said composition a)
The ethylene-alpha-olefin-nonconjugated every parts by weight of 100 parts by weight 80 of diene copolymers (i), and
E) vulcanizing agent.
Component a)
Ethylene-alpha-olefin-nonconjugated diene copolymers (i)
The content of the preferred ethene of the ethylene-alpha-olefin-nonconjugated diene copolymers, more precisely ethylene unit contain
Amount is by weight the 48% to 65% of the polymer.Here, " unit " refers to the monomeric unit of polymerization.For example, " ethene list
Member " refers to the ethylene unit of polymerization.
The reality of the alpha-olefin of ethylene-alpha-olefin-nonconjugated diene copolymers included in component a) oil filling copolymer
Example is propylene, 1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene, 1- octenes and 1- decene.Among those, propylene
It is preferred with 1- butylene.Propylene is most preferred.
Especially, the alpha-olefin content is the remainder to ethene and diene.Preferably, the C2/ alpha-olefin ratio is
From 73/27 to 40/60.
Preferably, " non-conjugated diene " of the copolymer refers to not only non-conjugated diene but also also unconjugated polyene,
Such as non-conjugated triolefin.The example of such compound is the unconjugated diene of straight chain, for example Isosorbide-5-Nitrae-hexadiene, 1,6- octadienes,
2- methyl isophthalic acids, 5- hexadienes, 6- methyl isophthalic acids, 5- heptadiene and 7- methyl isophthalic acids, 6- octadienes；The non-conjugated diene of ring-type, such as ring
Hexadiene, dicyclopentadiene, the indenes of methyl four, 5- vinyl norbornenes, 5- ethidine -2- ENBs and 6- chloromethyls -5-
Isopropenyl -2- ENBs；Triolefin, such as 2,3- diisopropyls fork base -5- ENBs, 2- ethidine -3- isopropylidenes -5- drops
Bornylene, 2- acrylic -2,2- norbornadienes, 1,3,7- sarohornenes and 1,4,9- last of the ten Heavenly stems triolefins；5- vinyl -2- norborneols
Alkene；5- (2- acrylic) -2- ENBs；5- (3- cyclobutenyls) -2- ENBs；5- (4- pentenyls) -2- ENBs；5-
(5- hexenyls) -2- ENBs；5- (5- heptenyls) -2- ENBs；5- (7- octenyls) -2- ENBs；5- methylenes
Base -2- ENBs；6,10- dimethyl -1,5,9- hendecane triolefins；5,9- dimethyl -1,4,8- last of the ten Heavenly stems triolefins；4- ethidines-
8- methyl isophthalic acids, 7- nonadienes；13- ethyl -9- methyl isophthalic acids, 9,12- pentadecane triolefins；5,9,13- trimethyls -1,4,8,12- ten
Four alkane diene；8,14,16- trimethyls -1,7,14- hexadecanes triolefin and 4- ethidine -12- methyl isophthalic acids, 11- pentadecane diene.
These compounds can be used alone or are applied in combination with two or more.It is preferred that compound be 5- ethidines -2- drop ice
Piece alkene or dicyclopentadiene or combination.
Preferably, the diene content is by weight the 3% to 7% of ethylene-alpha-olefin-nonconjugated diene copolymers.
The ethylene-alpha-olefin-nonconjugated diene copolymers (i) preferably have at least 300 by high temperature gpc measurement,
000g/mol, at least 400,000g/mol preferably, Weight-average molecular especially from 400,000g/mol to 700,000g/mol
Measure (Mw).Inherent viscosity in 70 DEG C of measurements in dimethylbenzene will be preferably at least 4.2.
Ethylene-alpha-olefin-nonconjugated diene copolymers included in the oil-filled composition pass through High Temperature Gel Permeation
The polydispersity of chromatography measurement, i.e. weight average molecular weight/number-average molecular weight, is the model 2 to 2.8, preferably 2 to 2.5
In enclosing.
Extending oil (ii)
" extending oil " used in component a) preferably refers to the oil-extender commonly used in oil-extended rubber is produced.Should
The example of extending oil be paraffin, cycloalkanes and the higher boiling by purifying (and if necessary be processed further) oil
The aromatic series extending oil that cut is obtained.These extending oils are generally shown at 100 DEG C from 5 to 35mm2/ s dynamic viscosity.It is excellent
The processing oil of choosing is the processing oil of paraffin.Suitable paraffin oil is for example obtainable from Suncor Inc. (CA) 500-4th Avenue S.W., Calgary, Alberta, T2P2V5. Canada (Sunoco)2280 or transparent paraffin oil pictures are obtainable from the international Oil Co., Ltd (ConocoPhillips) of Kang Fei12P.The oil being made via gas to liquid (GTL) method, such as from Shell Co. Ltd (Shell)X 430 is also preferred.
Auxiliary agent (iii)
Auxiliary agent is the other composition of oil-filled ethylene-alpha-olefin-nonconjugated diene copolymers, as antioxidant (such as comes from
BASF AG (BASF)1076), UV stabilizer, distribution agent or processing aid are (as talcum or metal salt (example
Such as the stearate as zinc, magnesium or calcium), these auxiliary agents will be remained in the rubber after fabrication.Their content sum is excellent
Selection of land is even at a fairly low, the ethylene-alpha-olefin-nonconjugated diene copolymers (i) of every 100 parts by weight specifically from 0 to 2, it is optimal
Selection of land is from 0 to 1 parts by weight.
Phase angle δmin
Phase angle δminKnown to those skilled in the art, such as in S.Trinkle and C.Friedrich, rheology
Journal (Rheol.Acta) 40:322-328,2001 and M.van Gurp and J.Palmen, rheology circular magazine
(J.Rheol.Bull.), 67:5-8, in 1998.δminValue is the compound quantity for including following polymer property, such as molecule
Amount, monomer distribution, polydispersity, long chain branching and increment oil concentration.By combing these characteristics in single parameter, use
δminTo characterize the intrinsic dynamic characteristic of the isolation mounting based on EPDM.Routine side well known by persons skilled in the art can be passed through
Method determines phase angle δmin, for example, referred in above-mentioned article.Specifically, the measurement is as follows：10-2Hz is extremely
103In the range of Hz under the logarithmic scale of every ten 8 data point frequencies (have) respectively -60, -50, -40, -30, -20, -
10th, 0,10,20,40,60,80, perform a scan under 100 and 120 degrees Celsius.In order to ensure applied stress and deformation be
In the limit of linear viscosity, if the deformation of sample is equal to or less than 0.5 μm, apply 0.5N constant force.Otherwise 0.5 is used
μm constant deformation.Vibration measurement discloses modulus of shearing, G* and loss factor, tan (δ) magnitude.By by phase angle δ
It is right | G* | draw, obtain van Gurp-Palmen curve maps.Minimum δ (| G* |) it is shown as δmin.Phase angle δminPreferably
It is less than 2.3.
Component a) oil-filled ethylene-alpha-olefin-nonconjugated diene copolymers composition preferably has 50MU and 90MU, spy
Other ground 60MU to 80MU 150 DEG C of Mooney (Mooney) viscosity ML (1+8).
Method
One kind is used to produce the ethylene-alpha-olefin-nonconjugated diene copolymers included in component a) oil filling copolymer
(i) method is not particularly limited.It can use for example conventional urging based on vanadium by slurry, solution or gaseous polymerization
Agent or metallocene or post-metallocene catalyst are produced.Suitably method and catalyst is known in the literature.
Component a) oil-filled EPDM composition can by wherein by the extending oil and this ethylene-alpha-olefin-nonconjugated two
Method that alkene copolymer (i) is blended during its production stage is produced.The addition preferably take place after the reactor but
Before volatile matter is removed, such as before steam stripping tower.More specifically, it by wherein by the extending oil and the ethene-α-
The method of alkene-non-conjugated diene copolymer (i) blending is produced, and the copolymer is dissolved or suspended in from the polymerisation
In the reaction medium of device.Therefore, reason be in the case of the oil is added later because the ethene-α used in the present invention-
The HMW of alkene-non-conjugated diene copolymer (i), may lead to not the copolymer and the extending oil is fully blended.
Component b)
The diene rubber component b) of the present invention preferably includes those based on dienes, and specific example is in main chain
Comprising double bond and actually do not include the rubber of gel content, and DIN/ISO1629 is named as R rubber.Preferably use
The examples of rubber components be those based on the following：Natural rubber (NR), polyisoprene (IR), styrene/fourth two
Alkene rubber (SBR), polybutadiene rubber (BR), styrene/isoprene rubber (SIBR), nitrile rubber (NBR), butyl rubber
Glue, isobutene/isoprene rubber (IIR), the nitrile rubber (HNBR) of hydrogenation, phenylethylene/butadiene/acrylic-nitrile rubber
(SNBR), polychlorobutadiene (CR), the styrene/butadiene rubbers (XSBR) of carboxylation, the butadiene/acrylonitrile rubber of carboxylation
(XNBR), epoxidized natural rubber (ENR), epoxidised styrene/butadiene rubbers (ESBR) and these rubber is mixed
Compound.
In the present invention, component b) preferred rubber components are to be selected from the group being made up of NR, IR, SBR and BR at least
It is a kind of.
Particularly preferred natural rubber (NR), the polyisoprene (IR) of synthesis and polybutadiene rubber (BR) and also benzene
Ethene/dience rubber, particularly styrene/diene rubbers, particularly styrene/butadiene rubbers, and also have these rubbers
The mixture of glue.
By rubber tree (Hevea Brasiliensis) and its subspecies natural rubber (NR) is collected as latex.Recently, also
Guayule rubber (Guayule) and Russian dandelion (Russian dandelion) has been planted to produce for NR.
The NR producer preferably Southeast Asia such as Malaysia, Indonesia, Thailand, Vietnam, India, China and
Found in many other Asia, Africa and American States.
The original NR such as condensed by latex can contain impurity in addition to hydrocarbon component.The amount of impurity depend on source and
Condensation process condition, and 15% can be increased up to, typically between 2%-10%.
NR rubber hydrocarbon component is preferably made up of (straight chain) cis -1,4- polyisoprene more than 99%.Gather in NR
The mean molecule quantity of isoprene is preferably from 100,000-600,000, more particularly from 200,000-400,000 scope
It is interior.
Preferably, using the NR grades for the group for belonging to specificationrubber.Example is the rubber of SMR and SVR types.These
It is according to dirt, ash content and the nitrogen content divided rank in addition to volatile materials and so-called plasticity retention index (PRI)
's.According to ISO 2930:The 1995 suitable PRI values determined are between 20 to 80.
It is highly preferred that viscosity stabilization grade and the Mooney between 20-100MU measured at 100 DEG C
Scope is used together, such as SMR CV 60 or SVR CV 60.
The polyisoprene (IR) of synthesis preferably has at least 70% 1,4- cis-contents.IR by lithium catalyst or
(Hao Ben-Wei Er, organic chemistry procedures (Methoden der are normally synthesized under the auxiliary of Ziegler/Natta catalyst
Organischen Chemie), Di Mu publishing houses, Stuttgart, 1987, E volumes 20, page 114 to 134；The work of Liv Ullmann
Industry chemistry is encyclopaedical (Ullmann ' s Encyclopedia of Industrial Chemistry), the A23 volumes, rubber 3.
Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Wei Yin Haimu, 1993, the 239-364 pages).IR also includes
The polyisoprene of referred to as 3,4- polyisoprene, it has the glass transition temperature in the range of -20 DEG C to+30 DEG C.
IR molecular weight is typically high, in the range of 1,000,000-2,000,000.It is highly preferred that at 100 DEG C
Mooney scope be from 50-150MU.
Styrene/dience rubber (particularly butadiene rubber) refer not only to solution S BR rubber (being abbreviated as SSBR) and
Also refer to emulsion SBR rubber (being abbreviated as ESBR).SSBR refers to the rubber-like polymer produced in solwution method, and they are to be based on second
Alkenyl aromatic compound and conjugated diene (H.L.Hsieh, R.P.Quirk, Marcel De Ke companies (Marcel Dekker
Inc) New York Basel 1996；I.Franta, elastomer and rubber compounded materials (Elastomers and Rubber
Compounding Materials)；Elsevier (Elsevier), 1989,73-74,92-94 page；Hao Ben-Wei Er, it is organic
Chemical method (Methoden der Organischen Chemie), Di Mu publishing houses, Stuttgart, 1987, E volumes 20,
Page 114 to 134；Industrial chemistry encyclopaedia (Ullmann ' the s Encyclopedia of Industrial of Liv Ullmann
Chemistry), the A23 volumes, the synthetic of rubber 3., VCH Verlagsgesellschaft mbH, D-69451 Wei Yin Haimu,
1993, the 239-364 pages of S. and also have (FR 2 295 972)).Suitable vinyl aromatic monomers be styrene,
O-, m- and p-methylstyrene, industrial methyl styrene mixture, p-tert-butylstyrene, α-methylstyrene, to methoxy
Base styrene, vinyl naphthalene, divinylbenzene, trivinylbenzene and divinyl naphthalene.Optimization styrene.Copolymerizable vinyl groups
The content of aromatic compound is preferably by weight from 5% to 50%, more preferably by weight from 10% to 40%.Suitable
Alkadienes be 1,3- butadiene, isoprene, 1,3- pentadienes, 2,3 dimethyl butadiene, 1- phenyl -1,3- butadiene, with
And 1,3- hexadienes.Preferably 1,3- butadiene and isoprene.The content of the diene of copolymerization for by weight from 50% to
95%, preferably by weight from 60% to 90%.Copolymerization diene medium vinyl content be from 10% to 90%, and 1,
The content of 4- trans double bonds is that from 20% to 80%, and the content of Isosorbide-5-Nitrae-cis-double bonds is and vinyl and Isosorbide-5-Nitrae-trans double bond
It is overall complementary.SSBR contents of ethylene is preferably>20%.
The monomer of these polymerizations and different alkadienes configurations generally have random distribution in the polymer.SSBR
(A) definition is also aimed to including the rubber with block type structure, these rubber be referred to as integrated rubber (K.-H.Nordsiek,
K.-H.Kiepert, GAK Kautschuk Gummi Kunststoffe 33 (1980), the 4th phase, 251-255).
SSBR is not only intended to indicate that linear rubber, is also represented by the rubber of side chain or terminal groups modification.By way of example, refer to herein
FR 2 053 786 and JP-A-56-104 906.Used branching agent preferably includes silicon tetrachloride and butter of tin.
SSBR is produced especially by anionic solution polymerization, i.e., by means of in organic solvent based on alkali metal base or
Catalyst Production based on alkaline-earth metal.
Vinyl aromatic compounds/the dience rubber polymerizeing in the solution advantageously has from 20 to 150 Mooney lists
Position Mooney point, preferably from 30 to 100 mooney units.
ESBR refer to produce in emulsion method based on vinyl aromatic compounds, conjugated diene and (as appropriate)
Rubber-like polymer (industrial chemistry encyclopaedia (Ullmann ' the s Encyclopedia of of Liv Ullmann of other monomer
Industrial Chemistry), the A23 volumes, the synthetic of rubber 3., VCH Verlagsgesellschaft mbH, D-
69451 Wei Yin Haimu, 1993, the 247-251 pages).Vinyl aromatic compounds be styrene, p-methylstyrene and
α-methylstyrene.Two hydro carbons are specifically butadiene and isoprene.Other monomer is specifically acrylonitrile.Vinyl aromatic
The content of compound is by weight from 10% to 60%.Glass transition temperature is from -50 to+20 DEG C (being determined by DSC),
And Mooney point is from 20 to 150 mooney units.Specifically, with Mooney point>80MU HMW ESBR grades can be with
Rubber based on 100 parts by weight includes the oil of 30 to 100 parts by weight.The SSBR rubber of oil-containing does not have by differential thermal analysis
(DSC) glass transition temperature determined by from -80 DEG C to+20 DEG C.
Polybutadiene (BR) specifically includes two kinds of different classes of polybutadiene.The first kind is suitable with the 1,4 of at least 90%
Formula content, and produced with the help of Ziegler/Natta catalyst based on transition metal.Preferably use based on Ti,
Ni, Co and Nd catalyst system (Hao Ben-Wei Er, organic chemistry procedures (Methoden der Organischen
Chemie), Di Mu publishing houses, Stuttgart, 1987, E volumes 20, page 114 to 134；The industrial chemistry encyclopaedia of Liv Ullmann is complete
Book (Ullmann ' s Encyclopedia of Industrial Chemistry), the A23 volumes, the synthetic of rubber 3., VCH
Verlagsgesellschaft mbH, D-69451 Wei Yin Haimu, 1993, the 239-364 pages).The glass of this polybutadiene
Change transition temperature to be preferably<- 90 DEG C (being determined by DSC).
The polybutadiene of Equations of The Second Kind is using Li Catalyst Productions and with the contents of ethylene from 10% to 80%.
The glass transition temperature of these polybutadiene rubbers is in the range of -90 DEG C to+20 DEG C (being determined by DSC).
The mean molecule grade of suitable BR grades is in the range of 100,000-500,000, wherein corresponding Mooney
Scope be at 100 DEG C between 20-100, more particularly between 30-75.
Component c) fillers
The amount that preferably filler is used is every 100 weight of ethylene-alpha-olefin-nonconjugated diene (i) based on component a)
Measure the parts by weight of part 50 to 80.It is preferred that filler be the carbon black or inorganic filler for being routinely used for rubber, such as silica,
Calcium carbonate, talcum and clay.The type of carbon black is (with m according to ASTM D-1765 for its particle size2The BET of/g meters) and
Structure is (with cm3The DBP absorption of/100g meters) classification.Carbon black-filled dose preferably used have from 5 to 150 BET numbers and
From 30 to 140 DBP numbers.These types of carbon black are named frequently by abbreviation in the industry, such as MT, SRF, GPF, FEF,
HAF、ISAF、SAF.These inorganic fillers can be surface-treated with for example suitable silane.Two kinds or more can be used
The combination of a variety of such fillers.Most preferably be carbon black and/or silanization silica.
Component d) operation oil
It can use with extending oil identical oil as operation oil.In addition, as operation oil it can be mentioned that lubricating oil, stone
Wax, atoleine, asphalt, vaseline, low molecule amount polyisobutene or polybutene, liquid EPDM or EPM, coal tar drip
Green grass or young crops, castor oil, linseed oil, beeswax, random polypropylene and benzofuran indene resin.However, when the oil-filled EPDM composition
When extending oil can be enough to be used in the purpose of the present invention, it is not necessary to add other oil to form the vulcanizable building rubber compound
Thing.If so, total oil content should be restricted to the ethylene-alpha-olefin-nonconjugated diene copolymerization based on EPDM composition a)
Every 100 parts of parts by weight 80 parts by weight of thing (i).It is preferably based on the ethylene-alpha-olefin-nonconjugated diene copolymers (i) every 100
Parts by weight add the paraffinic extender oil of 5 to 15 parts by weight.This paraffin oil can be made according to GTL methods.
Component e) vulcanizing agents
The example of vulcanizing agent is sulphur；Sulfur chloride；Sulfur dichloride；4,4 '-dithio morpholine；Morpholine disulfide；Curing
Alkyl phenol；Tetramethylthiuram disulfide；Selenium dimethyl dithiocarbamate；And organic peroxide, for example cross dicumyl
Peroxide, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, (benzoylperoxies of 2,5- dimethyl -2,5- two
Base)-hexane, 2,5- dimethyl -2,5- (t-butylperoxy) hexin -3, di-tert-butyl peroxide, di-tert-butyl peroxide
Thing -3,3,5- trimethyl-cyclohexanes and tert-butyl hydroperoxide.Among those, preferably sulphur, dicumyl peroxide,
Di-tert-butyl peroxide and tert-butyl peroxide -3,3,5- trimethyl-cyclohexanes.
In the case of sulfur curable, sulphur is preferably with the ethylene-alpha-olefin-nonconjugated diene (i) of every 100 parts by weight
0.1 to 10 parts by weight and amount preferably from 0.5 to 5 parts by weight is used.
In the case of peroxide cure, the organic peroxide is typically with the copolymer of every 100 parts by weight
Amount from 0.1 to 15 parts by weight and preferably from 0.5 to 8 parts by weight is used.
Vulcanizing agent can be used, if necessary, is combined with vulcanization accelerator and vulcanization active additive.The vulcanization accelerator
Example is N- cyclohexyl -2-[4-morpholinodithio-sulfenamide, N- oxygen diethylidene -2-[4-morpholinodithio-sulfenamide, N, and N- bis- is different
Propyl group -2-[4-morpholinodithio-sulfenamide, 2-mercaptobenzothiazole, 2- (dinitrophenyl group) mercaptobenzothiazoler, 2- (2,
6- diethyl -4- morpholinoes are thio) benzothiazole, bisbenzothiazole base-disulphide, diphenylguanidine, triphenyl guanidine, di-o-tolyl
Guanidine, o-tolyl-biguanide, diphenylguanidine-phthalic acid ester, acetaldehyde-aniline reaction product, the condensate of butyraldehyde-aniline, six Asias
Tetramine, acetaldehyde close amine, 2- mercaptoimidazolines, thio acardite, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, two
O-tolyl thiocarbamide, single vulcanization tetra methylthiuram, tetramethylthiuram disulfide, tetraethylthiuram disulfide, curing
Tetrabutyl thiuram, four vulcanization two amyl- methyl-alkenyl thiurams, PZ, diethyl sulfo-amino
Zinc formate, di-n-butyl zinc thiocarbamate, zinc-ethylphenyl dithiocarbamate, butyl phenyl aminodithioformic acid
Zinc, methyl disulfide amine sodium formate, methyl disulfide amine formic acid selenium, diethyl thiamine disulfide formic acid tellurium, dibutyl xanthic acid zinc and sub- second
Base thiocarbamide.If used, the vulcanization accelerator is preferably with the ethylene-alpha-olefin-nonconjugated diene of every 100 parts by weight
(i) from 0.1 to 20 parts by weight and especially the amount from 0.2 to 10 parts by weight is used.
The example of vulcanization aid is metal oxide, such as magnesia and zinc oxide.Among those, preferably aoxidize
Zinc.The usually used amount of the vulcanization aid is the component a) of every 100 parts by weight ethylene-alpha-olefin-nonconjugated diene (i) from 2
To 20 parts by weight.
When peroxide is used as vulcanizing agent, the example of crosslinking coagent or activator is cyanurate compound, and such as cyanogen is urinated
Sour triallyl (TAC) and the chlorinated isocyanurates of trialkenyl third (TAIC), such as (methyl) acrylate compounds, trihydroxy methyl third
Alkane-trimethyl acrylic ester (TMPT or TRIM) and ethylene glycol dimethacrylate (EDMA), zinc dimethacrylate
(ZDMA) it is and diacrylate zinc (ZDA), divinylbenzene, paraquinonedioxime, metaphenylene dimaleimide (HVA-2), (high
Vinyl) polybutadiene and combinations thereof.When using peroxide as vulcanizing agent, furthermore, it is possible to be preferably used
Sulphur (element or the part as sulphur accelerator or donor) is to obtain so-called mixing cured system.These firming body tyings
Closed hyperpyrexia resistance characteristics (being typically used for peroxide cure), and extraordinary final response, such as stretch and tear and
Outstanding dynamic and fatigue properties (typically associated with sulfur curable system).The dosage level of the sulphur applied preferably base
In ethylene-alpha-olefin-nonconjugated every 100 parts by weight of diene copolymers (i) from 0.05 to 1.0 parts by weight, preferably from 0.2 to
0.5 parts by weight.
In addition the compositions of vulcanize rubbers may also contain other compositions, such as antioxidant (such as TMQ),
Drier (such as CaO), tackifier (tackyfier) (for example, resin), adhesive, pigment, processing aid (such as ointment, fat
Fat acid, stearate, poly- or two-ethylene glycol).
The invention further relates to it is a kind of by the present invention vulcanize the vulcanized rubber article that rubber composition is made.This vulcanization
Rubber is preferably engine bracket.
The invention further relates to a kind of method for forming vulcanized rubber article, this method includes processing according to the present invention's
Rubber composition is to form the net shape of molded products and the step of solidify the rubber composition.
For example, this method preferably includes following steps：(i) with conventional kneader (such as open roll mill, banburying
Machine, kneader and extruder) mediate oil-filled EPDM composition a), component b) diene rubber, vulcanizing agent, filler and (such as
Fruit needs) above-mentioned other compositions, to obtain the product of mixing, and (ii) vulcanizes kneading obtained by (crosslinking) under heating
Product.Such a mixed process can be carried out in one or more steps, as is known to persons skilled in the art.
Vibration-proof rubber product can be best suited for according to the vulcanized rubber article of the present invention, such as engine bracket and muffler are hung
Frame is intended to for other products in dynamic application, such as flexible coupling and torsional vibration damper also have belt, air spring with
And bridge seat.
Example
Measurement
Phase angle δ
Rheology is completed using the DMA/STDA861e instruments from plum Teller-support benefit (Mettler-Toledo) to survey
Amount.These EPDM samples have 1 millimeter of thickness and 6 millimeters of diameter.Two samples are symmetrically mounted at double-shear interlayer
In specimen holder.Using liquid nitrogen and electric heater by the accuracy of the temperature control of the smelting furnace to 0.5 Kelvin.It is poly- in order to characterize
Compound dynamic characteristic, from 10-2To 103In the range of Hz the logarithmic scale of every ten 8 data point frequencies (have) respectively-
60th, -50, -40, -30, -20, -10,0,10,20,40,60,80, perform a scan under 100 and 120 degrees Celsius.It is additional to answer
Power and deformation are in the limit of linear viscosity.If the deformation of sample is equal to or less than 0.5 μm, apply 0.5N perseverance
Power.Otherwise using 0.5 μm of constant deformation.Vibration measurement discloses modulus of shearing, G* and loss factor, tan (δ) magnitude.
Phase angle δ is right | G* | drawing gives so-called van Gurp-Palmen (vGP) curve map as can be seen in Figure 1.
Referring further to M.van Gurp, and J.Palmen, rheology circular magazine (J.Rheol.Bull.), 67:5-8,1998.
Fig. 1 shows the modified EDPM of the oil of example 1 vGP curve maps.The vGP curve maps clearly illustrate δ (| G* |)
Minimum value.Minimum value δminIt is the compound quantity for including following polymer property, such as molecular weight, polydispersity, long chain branching
(referring to S.Trinkle and C.Friedrich, rheology journal (Rheol.Acta) 40:322-328,2001) and extending oil
Concentration.
Example 1
Oil-filled polymer a) preparation：
The trimer of ethene, propylene and 5- ethidine -2- ENBs (ENB), the catalysis are produced using catalyst system
Agent system includes the sour vanadium (V (acac) of praseodynium3) make as catalyst, alkyl aluminium halide (diethylaluminum chloride (DEAC))
It is that co-catalyst and ethyl trichloroacetate (ETA) are used as catalyst activator.The C2/C3 ratios and diene content of copolymer
It can see from table 1.
Continuous polymerization reaction equipped with stir and be equipped with the reactor of evaporation-cooled device carry out.First to this
Load propylene, ENB, ethene and butane in reactor, and these reactor contents is balanced at a temperature of 12 DEG C.Will be from
The volatile matter of evaporation-cooled device condensation is sent back in the reactor.Then cleaned using the bed with 3A and 13X molecular sieves
And dry a fluid stream and remove the impurity especially aoxidized, the impurity of these oxidations will reduce catalytic activity and polymer is special
Property.
Then by 0.2 weight in the DEAC solution and toluene of 1 percentage by weight in the continuous stream of gaseous ethylene, hexamethylene
The V (acac) of percentage3Solution is (in addition also containing activator and vanadium 4:The activator of 1 molar ratio) to be fed to this anti-
Answer in device.DEAC and V (acac)3Molar ratio be 22 to 1.
The pressure cycle of these reactor contents is adjusted to about 71psig to maintain temperature at 12 DEG C.From adding
Enter catalyst and co-catalyst stream starts, the starting of the reaction generally takes 10-20 minutes.Hereafter, the reactor is placed in tool
There is the continuous mode of operation of continuous monomer stream.Mooney is controlled by adding about 100ppm zinc ethide.
Used reactor feed formula is the molar ratio based on the various components for 100 mol propylenes and will
It is listed in table 1.The mean residence time of these reactants is 1 hour.The polymer paste is collected in the appearance containing water
In device.Meanwhile, by the solution and transparent extending oil of Irganox 1076 in hexane12P is according to following
Amount be continuously added in the container, the final oil-extended rubber is that oil content is 50phr and the contents of Irganox 1076 are
Based on the every parts by weight of 100 parts by weight 0.3 of the ethene-alpha-olefin non-conjugated diene copolymer (i).
Then with the steam stripping polymer paste to remove remnants hydrocarbon and then dry polymer product.For it
Composition and Mooney viscosity, analyze the polymer produced by the above method.
Mw is 470kg/mol, it is found that Mn is 205kg/mol.Polydispersity (PDI) is 2.3.δminIt is 1.9.Mooney viscosity
150 DEG C of ML (1+8) is 67MU.The polymer samples of example 1 show the spy in 70 DEG C of 4.4 (dl/g) measured in dimethylbenzene
Property viscosity.
* is in 135 DEG C of intrinsic viscosities measured in naphthalane.
The preparation of compositions of vulcanize rubbers
Composition：
It is prepared for the various compositions of vulcanize rubbers based on different oil-filled EPDM compositions.Use is listed in table 2
In the composition of various Compound Evaluations.
Table 2- compositions are summarized
In the laboratory banbury mixer (GK1,5E1 from Harburg-Freudenberger Maschinenbau GmbH；
The bar of stamping press 7,45rpm, 70% filling extent, incorporation time 4min) on prepare all compounds；Straight with 200mm
(1.22) 20rpm, 40 DEG C of roller temperatures, friction adds the chemicals of the cure system on the open pulverizer of the roller in footpath.
By solidifying the test sheet of 2mm and 6mm thickness at 180 DEG C, to the time equivalent to t95, (t95 is surveyed in MDR
The time of 95% peak torque is reached during amount) for all compounds prepare test specimen.
Measure various processing, physics and dynamic mechanically characteristic.The characteristic tested in various tests is according in table 3
The tests below method listed is measured.
The test method of table 3.：
Use the Dynamic mechanical analysis instrument from MTS.These samples are 6mm height and 20mm diameter.Using wherein
It is symmetrically installed the double-shear interlayer specimen holder of two samples.Before the start of the measurement, the specimen holder is placed on and be tempered to 23
DEG C smelting furnace in continue at least 30min.The linear viscoelasticity characteristic of these elastomeric materials be with single shear geometry for from
What the frequency (logarithmic scale with every ten 8 data points) in the range of 0.1Hz to 200Hz was measured.Apply 0.3mm peak
Between amplitude.
Dynamic tear analyzer
The measurement of fracture propagation is carried out with the tear analyzer from Ke Aisi Fils moral company (Coesfeld).70
The bar samples sample record data of 15 mm wides, 1.5 millimeters thicks and 65 millimeters of free suspension length is used at DEG C.With point
Sharp razor blade cuts breach (1 millimeter of notch length) to these samples.For each test-strips, definite sample is determined thick
Degree.By sample 4Hz pulse recurrence rate uniaxial tension.With the harmonic modulation arteries and veins with 30Hz frequencies and 20% to 30% amplitude
Punching.The termination in life-span is reached when crack length is 10 millimeters.
Mixture result；Example 1：
It is vulcanizable based on what is be such as given in Table 4 based on various oil-filled EPDM to compare to carry out various experiment tests
The characteristic of the vulcanizate of rubber composition, is particularly contemplated as based on such as the Keltan defined in WO03/020806
DE304 and Vistalon 8800 rubber composition.
Table 4：Rubber stiffness and enhancing
Key Performance Indicator for rubber mount is vibration isolation, i.e., under the stress of restriction and for given frequency model
Enclose minimum possibility loss angle δ (or Tan δ measured by MTS, see the above table).In other words, tan δ values are zero to refer to " ideal " bullet
Property material.This material shows high resilience value, it is generally desirable to 100%.
Important design parameter is the rigidity (or " spring constant ") of rubber mount, in fact, it often refers to rubber
Hardness or modulus (tangent line i.e. in stress/strain curves zero stress at) of the material under low elongation.Therefore for identical
Rigidity (i.e. hardness level) should ideally carry out dynamic property comparison.In EPDM compoundings, by suitable filler (such as
Carbon black) enhancing mechanism realize required firmness level.It is well known, however, that to be that high-caliber carbon black causes higher
Tan δ values and worse anti-vibration performance.
In all cases it is possible to obtain with some low δminThe oil-filled EPDM according to the present invention of value relative dynamic
Performance, the EPDM types of optimal anti-vibration performance.
Mixture example 2
In order to further improve fatigue behaviour, R rubber is added as component b).
In example 2 below, three kinds of different R rubber are added：
a)NR-SVR CV 60.This is the example of the natural rubber for the group for belonging to the specificationrubber produced in Vietnam.
Mooney viscosity at 100 DEG C is 60+/- 5MU.
b)S-SBR-Buna SL 4515-0.This is to be produced containing 25% use alkyl lithium catalyst by polymerisation in solution
Styrene SB example.Mooney viscosity at 100 DEG C is 45MU.
c)BR-Buna CB24.This be the solution that is produced with neodymium catalyst it is high-cis (>96%) polybutadiene polymers
Example.Mooney viscosity at 100 DEG C is 44MU.
In table 5, the preparation of the addition with R rubber and the reference preparation of the addition without R rubber are compared
Compared with.It is expressly noted that, the addition of R rubber is with for such as by tearing the unexpected of the spreading property of tear that analyzer is measured
Pretend use in ground.
On additional stress level, from 20,000 circulations until 83,000 circulations are significantly improved following until failure
Number of rings mesh, i.e. fatigue life.
Table 5. improves the example of the EPDM preparations of the addition R rubber of fatigue life (until the number of cycles of failure)
Claims (10)
1. a kind of compositions of vulcanize rubbers, comprising：
A) the oil-filled copolymer compositions being made up of the following
I) 100 parts of at least one ethylene-alpha-olefin-nonconjugated diene copolymers with the following
- at least 300,000g/mol weight average molecular weight (Mw).
- measured in dimethylbenzene at 70 DEG C higher than 4, be preferably higher than 4.2 inherent viscosity, and
- be less than 3, be preferably less than 2.8, particularly less than 2.6 polydispersity (Mw/Mn)；
Ii) the extending oil of every 100 parts by weight ethylene-alpha-olefin-nonconjugated parts by weight of diene copolymers (i) 30 to 70, and
Iii) every 100 parts by weight ethylene-alpha-olefin-nonconjugated diene copolymers (i) are up to the auxiliary agent of 5 parts by weight,
Thus the oil-filled copolymer compositions have the phase angle δ less than 2.5min,
B) the every weight of 100 parts by weight 1 to 15 of ethylene-alpha-olefin-nonconjugated diene (i) based on the oil-filled copolymer compositions a)
The unsaturated rubber for being named as R rubber according to DIN/ISO 1629 of part is measured,
C) every 100 parts by weight 30 to 100 of ethylene-alpha-olefin-nonconjugated diene (i) based on the oil-filled copolymer compositions a)
The filler of parts by weight,
D) said composition a) the every parts by weight of 100 parts by weight 0 to 30 of ethylene-alpha-olefin-nonconjugated diene copolymers (i) are based on
Operation oil, with the proviso that the total amount of the extending oil from said composition a) and operation oil is no more than the second based on said composition a)
The every parts by weight of 100 parts by weight 80 of alkene-alpha-olefin-nonconjugated diene copolymers (i), and
E) vulcanizing agent.
2. rubber composition according to claim 1, the wherein ethene-alpha-olefin of the oil-filled copolymer compositions a)-
The ethylene unit of non-conjugated diene (i) and the ratio of alpha-olefin unit are from 73/27 to 40/60.
3. the rubber composition according at least one in claim 1 to 2, the wherein oil-filled copolymer compositions a's)
The non-conjugated diene of ethylene-alpha-olefin-nonconjugated diene (i) is to be selected from the group, and the group is made up of the following：1,4- oneself two
Alkene, 1,6- octadienes, 2- methyl isophthalic acids, 5- hexadienes, 6- methyl isophthalic acids, 5- heptadiene and 7- methyl isophthalic acids, 6- octadienes；Ring-type it is non-
Conjugated diene, such as cyclohexadiene, dicyclopentadiene, the indenes of methyl four, 5- vinyl norbornenes, 5- ethidine -2- ENBs
With 6- chloromethyl -5- isopropenyl -2- ENBs；Triolefin, such as 2,3- diisopropyls fork base -5- ENBs, 2- ethidines -3-
Isopropylidene -5- ENBs, 2- acrylic -2,2- norbornadienes, 1,3,7- sarohornenes and 1,4,9- last of the ten Heavenly stems triolefins；5- ethene
Base -2- ENBs；5- (2- acrylic) -2- ENBs；5- (3- cyclobutenyls) -2- ENBs；5- (4- pentenyls) -2-
ENB；5- (5- hexenyls) -2- ENBs；5- (5- heptenyls) -2- ENBs；Ice drops in 5- (7- octenyls) -2-
Piece alkene；5- methylene -2- ENBs；6,10- dimethyl -1,5,9- hendecane triolefins；5,9- dimethyl -1,4,8- the last of the ten Heavenly stems three
Alkene；4- ethidine -8- methyl isophthalic acids, 7- nonadienes；13- ethyl -9- methyl isophthalic acids, 9,12- pentadecane triolefins；5,9,13- trimethyls-
1,4,8,12- tetradecadienes；8,14,16- trimethyls -1,7,14- hexadecanes triolefin and 4- ethidine -12- methyl isophthalic acids, 11-
Pentadecane diene, preferably 5- ethidines -2- ENBs.
4. the rubber composition according at least one in claims 1 to 3, the wherein oil-filled copolymer compositions a's)
The alpha-olefin of ethylene-alpha-olefin-nonconjugated diene (i) is to be selected from the group, and the group is made up of the following：Propylene, 1- butylene, 1-
Amylene, 1- hexenes, 4-methyl-1-pentene, 1- octenes and 1- decene, preferably propylene.
5. the rubber composition according at least one in Claims 1-4, the wherein oil-filled copolymer compositions a's)
Extending oil is selected from the group, and the group is made up of the following：Paraffin, cycloalkane and the high boiling fraction acquisition by purifying oil
Aromatic series extending oil.
6. the rubber composition according at least one in claim 1 to 5, wherein component b) unsaturated rubber is selected from
The following group, the group is made up of the following：It is natural rubber (NR), polyisoprene (IR), styrene/butadiene rubbers (SBR), poly-
Butadiene rubber (BR), styrene/isoprene rubber (SIBR), nitrile rubber (NBR), butyl rubber isobutene/isoamyl two
Alkene rubber (IIR), the nitrile rubber (HNBR) of hydrogenation, phenylethylene/butadiene/acrylic-nitrile rubber (SNBR), polychlorobutadiene
(CR), styrene/butadiene rubbers (XSBR) of carboxylation, the butadiene/acrylonitrile rubber (XNBR) of carboxylation, epoxidised natural
The mixture of rubber (ENR), epoxidised styrene/butadiene rubbers (ESBR) and these rubber.
7. the rubber composition according at least one in claim 1 to 6, wherein component b) unsaturated rubber is choosing
At least one of the group of free NR, BR, SBR and IR composition.
8. a kind of vulcanization rubber by being made according to the described compositions of vulcanize rubbers of at least one in claim 1 to 7
Product.
9. vulcanized rubber article according to claim 8, wherein wherein the product is engine bracket.
10. a kind of method for forming vulcanized rubber article, this method includes processing according in claim 1 to 7 at least one
Rubber composition described in is to form the net shape of molded products and the step of solidify the rubber composition.
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| EP14196564.0A EP3029102A1 (en) | 2014-12-05 | 2014-12-05 | Vulcanizable rubber composition |
| EP14196564.0 | 2014-12-05 | ||
| PCT/EP2015/078666 WO2016087647A1 (en) | 2014-12-05 | 2015-12-04 | Vulcanizable rubber composition |
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| US (1) | US10150859B2 (en) |
| EP (2) | EP3029102A1 (en) |
| JP (1) | JP6622803B2 (en) |
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| CN (1) | CN107001742B (en) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110869434A (en) * | 2018-05-17 | 2020-03-06 | 株式会社Lg化学 | Rubber composition |
| CN111148641A (en) * | 2017-08-24 | 2020-05-12 | 陶氏环球技术有限责任公司 | ethylene/C5-C10 α -olefin/polyene interpolymers |
| CN111770956A (en) * | 2018-02-27 | 2020-10-13 | 阿科玛法国公司 | Use of magnesium oxide for crosslinking polymers |
| CN113853405A (en) * | 2019-06-21 | 2021-12-28 | 埃克森美孚化学专利公司 | Thermoplastic vulcanizate composition |
| CN114746503A (en) * | 2019-11-27 | 2022-07-12 | 米其林集团总公司 | Self-sealing composition for pneumatic articles |
| CN115746472A (en) * | 2022-10-21 | 2023-03-07 | 安徽佳先功能助剂股份有限公司 | Composite heat stabilizer containing dibenzoyl methane for PVC |
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| EP3029102A1 (en) * | 2014-12-05 | 2016-06-08 | Lanxess Elastomers B.V. | Vulcanizable rubber composition |
| CN109153832B (en) * | 2016-05-20 | 2021-03-02 | 阿朗新科荷兰有限公司 | Rubber composition |
| FR3058148A1 (en) * | 2016-10-31 | 2018-05-04 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION COMPRISING A SPECIFIC REINFORCING LOAD |
| KR20210064260A (en) * | 2018-09-26 | 2021-06-02 | 비를라 카본 유.에스.에이., 인코포레이티드 | Carbon black for improved automotive anti-vibration rubber compound performance |
| JP2023524448A (en) | 2020-05-15 | 2023-06-12 | アランセオ・ネザーランズ・ベー・フェー | ethylene-copolymer rubber |
| CN111607165B (en) * | 2020-06-24 | 2023-04-07 | 长缆电工科技股份有限公司 | High-expansion insulating ethylene-propylene rubber cold-contraction material, and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111148641A (en) * | 2017-08-24 | 2020-05-12 | 陶氏环球技术有限责任公司 | ethylene/C5-C10 α -olefin/polyene interpolymers |
| CN111770956A (en) * | 2018-02-27 | 2020-10-13 | 阿科玛法国公司 | Use of magnesium oxide for crosslinking polymers |
| CN110869434A (en) * | 2018-05-17 | 2020-03-06 | 株式会社Lg化学 | Rubber composition |
| CN110869434B (en) * | 2018-05-17 | 2022-02-25 | 株式会社Lg化学 | Rubber composition |
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| CN113853405A (en) * | 2019-06-21 | 2021-12-28 | 埃克森美孚化学专利公司 | Thermoplastic vulcanizate composition |
| CN114746503A (en) * | 2019-11-27 | 2022-07-12 | 米其林集团总公司 | Self-sealing composition for pneumatic articles |
| CN114746503B (en) * | 2019-11-27 | 2024-02-02 | 米其林集团总公司 | Self-sealing composition for inflatable articles |
| CN115746472A (en) * | 2022-10-21 | 2023-03-07 | 安徽佳先功能助剂股份有限公司 | Composite heat stabilizer containing dibenzoyl methane for PVC |
| CN115746472B (en) * | 2022-10-21 | 2023-10-20 | 安徽佳先功能助剂股份有限公司 | PVC composite heat stabilizer containing dibenzoylmethane |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3227384B1 (en) | 2019-02-20 |
| JP6622803B2 (en) | 2019-12-18 |
| CA2969581A1 (en) | 2016-06-09 |
| US20170313868A1 (en) | 2017-11-02 |
| KR20170095210A (en) | 2017-08-22 |
| BR112017011630A2 (en) | 2018-03-06 |
| CN107001742B (en) | 2020-01-31 |
| KR102434116B1 (en) | 2022-08-22 |
| EP3029102A1 (en) | 2016-06-08 |
| JP2018501344A (en) | 2018-01-18 |
| BR112017011630B1 (en) | 2022-03-03 |
| EP3227384A1 (en) | 2017-10-11 |
| WO2016087647A1 (en) | 2016-06-09 |
| US10150859B2 (en) | 2018-12-11 |
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